CA1193805A - Process for impregnating organic fibers - Google Patents
Process for impregnating organic fibersInfo
- Publication number
- CA1193805A CA1193805A CA000395942A CA395942A CA1193805A CA 1193805 A CA1193805 A CA 1193805A CA 000395942 A CA000395942 A CA 000395942A CA 395942 A CA395942 A CA 395942A CA 1193805 A CA1193805 A CA 1193805A
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- Prior art keywords
- bonded
- radicals
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- organic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
- D06M15/6436—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing amino groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/12—Polysiloxanes containing silicon bound to hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
- C08G77/16—Polysiloxanes containing silicon bound to oxygen-containing groups to hydroxyl groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2933—Coated or with bond, impregnation or core
- Y10T428/2962—Silane, silicone or siloxane in coating
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31652—Of asbestos
- Y10T428/31663—As siloxane, silicone or silane
Abstract
A PROCESS FOR IMPREGNATING ORGANIC FIBERS
Abstract of the Disclosure Organic fibers are impregnated with an aqueous emulsion comprising (1) an organopolysiloxane containing diorganosiloxane units in which both organic radicals are monovalent hydrocarbon radicals, and further contains at least two monovalent SiC-bonded organic radicals with a basic nitrogen atom per molecule in which the SiC-bonded organic radicals with a basic nitrogen are present in monoorganosiloxane units, (2) an organopoly-siloxane having at least 3 Si-bonded hydrogen atoms per molecule, (3) a catalyst for the condensation of Si-bonded condensable groups (4) emulsifiers, and (5) a diorganopolysiloxane containing an Si-bonded hydroxyl group in each of its terminal units and whose radicals are free of the basic nitrogen atom. If it is desired to impart hydrophobic properties to the impregnated organic fibers, then it is essential that (6) a trimethylsiloxy end-blocked diorganopolysiloxane be added to the aqueous emulsion.
Moreover, as the amount of trimethylsiloxy end-blocked diorgano-polysiloxane (6) is increased in the emulsion, the hydrophobic properties of the impregnated fibers increases.
When the aqueous emulsion is applied to keratin, especially wool, it prevents or reduces shrinkage due to felting, particularly when the keratin has been pretreated with chlorine, rinsed and neutralized.
Abstract of the Disclosure Organic fibers are impregnated with an aqueous emulsion comprising (1) an organopolysiloxane containing diorganosiloxane units in which both organic radicals are monovalent hydrocarbon radicals, and further contains at least two monovalent SiC-bonded organic radicals with a basic nitrogen atom per molecule in which the SiC-bonded organic radicals with a basic nitrogen are present in monoorganosiloxane units, (2) an organopoly-siloxane having at least 3 Si-bonded hydrogen atoms per molecule, (3) a catalyst for the condensation of Si-bonded condensable groups (4) emulsifiers, and (5) a diorganopolysiloxane containing an Si-bonded hydroxyl group in each of its terminal units and whose radicals are free of the basic nitrogen atom. If it is desired to impart hydrophobic properties to the impregnated organic fibers, then it is essential that (6) a trimethylsiloxy end-blocked diorganopolysiloxane be added to the aqueous emulsion.
Moreover, as the amount of trimethylsiloxy end-blocked diorgano-polysiloxane (6) is increased in the emulsion, the hydrophobic properties of the impregnated fibers increases.
When the aqueous emulsion is applied to keratin, especially wool, it prevents or reduces shrinkage due to felting, particularly when the keratin has been pretreated with chlorine, rinsed and neutralized.
Description
3~
A PROCESS FOR I~PRE~NATING ORGANIC FIBERS
The present invention relates to aqueous emulsions, particularly to aqueous emulsions which may be used for impreg-naking organic fibers. More particularlyl the invention relates t~ a process for impregnating fibers with an aqueous emulsion to impart a high degree of elasticity and a predetermined degree of hydrophobicity to the treated organic fibers.
Background of the Invention 9rganic fibers have been treated with aqueous emul sions containing polydiorganosiloxanes to impart hydrophobic propexties thereto. For example, U. S. Patent No. 4,098,701 to Burrill et al discloses treating organic fibers with an aqueous emulsion containing (A) an organopolysiloxane containing dior-ganosiloxane units in which the two organic radicals are mono-valent hydrocarbon radicals and further contains at least two monovalent SiC-bonded organic radicals with basic nitrcgen for each molecule, ~B) an organopolysiloxane having at least three silicon-bonded hydrogen atoms in the molecule and (C) a catalyst ~or the condensation of Si-bonded condensable groups.
In contrast to the processes known heretofore for txeating organic fibers, the process of this invention imparts not only a high degree of elasticity, but also a predetermined degree of hydrophobicity to the treated fibers. t~oreover, organic fibers treated in accordance with the process of thls invention have a high degree of dimensional stability and are easy to sew. Furthermore, all of the properties imparted to the treated organic fibers by the process of this invention ara preserved even when the fibers are washed with water or cleaned with organic solvents ~`~$3~
Therefore, it is an object of this invention to provide an aqueous emulsion for treating organic fibers~
Another object of this invention is to provide a process for treating organic fibers with an aqueous emulsior. to impart a high degree of elasticity to the treated fibers. Still another object of this invention is to provide a process for imparting a predetermined degree of hydrophobicity to the organic fibers. A
further object of this invention is to pxovide a process for imparting a high degree of dimensional stability to the treated O organic fibers. ~ - -~ ~~- `~- - ~
Swnmary of the In~ention The foregoing ob~ects and others which will become apparent from the following description are accomplished in accordance with this invention, generally speaking, by providing a process for impregnating organic fibers with an aqueous emul-sion comprising (l) an organopolysiloxane containing diorgano-siloxane units in which both organic radicals are monovalent hydrocarbon radicals, and also contains at least two monovalent SiC-bonded organic radicals per molecule with a basic nitrogen atom, in which the SiC-bonded organic radicals containing the basic nitrogen atom of the organopolysiloxane (l) are present in monoorganosiloxane units, (2~ an organopolysiloxane having at least 3 Si-bonded hydrogen atoms per molecule, (3) a catalyst for the condensation of Si-bonded condensable groups, (4) an emulsifier, (5) a diorganopolysiloxane containing an Si-bonded hydroxyl group in each of its terminal units, whose organic radicals are free of basic nitrogen atoms, and optionally (6) a trimethylsiloxy end-blocked diorganopolysiloxane having a vis-cosity of from about lO0 to lO,000 mPa.s at 25C.
Detailed Descrlption of the Invention Any organic fiber which has been or could have been impregnated heretofore with organopolysiloxanes can be impreg-nated with the aqueous emulsion of this invention.
Such organic fibers may be made of either natural or ~y~thetic fibers r- Suitable examples o organic fibers which may be ~reated by the process of this invention are fibers made of keratin, cotton, rayon, hemp, natural silk, polypropylene, polyethylene, polyester, polyurethane, polyamide, cellulose acetate and mixtures of such fibers. The fibers may be present --3~
in the form of fleeces, mats, ~abrics, knitted textiles, includ-ing articles of clothing or sections of clothing. Except for wool, it is preferred that the fibers be treated in the form of fabrics.
The amount of water present in these aqueous emulsions is not critical. It is, however, preferred that the total amount of water, in which the non-aqueous constitutents are dissolved or dispersed, range from about 35 to 90 percent by weight and more preferably rrom about 45 to 60 percent by ~eight, based on the total weight of the aqueous emulsion. These aqueous emulsions may be further diluted with water prior to application so that the amount of water will range from 60 to 99 percent by weight and more preferably from 80 to 95 percent by weight based on the total weight of the aqueous emulsion applied to the fabric.
The diorganosiloxane units present in the organopoly-siloxane (13 may be represented by the general formula R2Sib, in which R represents the same or different monovalent hydrocar bon radicals; preferably, having from 1 to 20 carbon atoms per radical. Examples of hydrocarbon radicals which may be present in the diorganosiloxane units of organopolysiloxane (1) are alkyl radicals, such as the methyl, ethyl, n-propyl and isopropyl radicals, as well as the butyl, octyl, tetradecyl and octadecyl radicals; alkenyl radicals such as the vinyl and the allyl radicals, as well as the hexenyl radicalsi cycloaliphatic hydro-carbon radicals, such as the cyclopentyl and the cyclohexyl radicals; aromatic hydrocarbon radicals such as the phenyl and the naphthyl radicals; alkaryl radicals such as the tolyl radicals and aralkyl radicals such as the benzyl radical.
Because of their availability, it is preferred that at least 80 percent of the number of hydrocarbon radicals in the diorgano-~iloxane units of organopolysiloxane (1) be methyl radicals.
The monoorganosiloxane units and the SiC-bonded organic radicals having a basic nitrogen atom which are present in the organopolysiloxane (1), may ke represented by the following general formula R2NR (R o)aSiO3_a I the above formula Rl represents a bivalent hydrocarbon radical, -R represents hydrogen or the same or different alkyl or amino-alkyl radicals, ~3 represents the same or different al};enyl radicals having from 1 to ~ carbon atoms per radical, and a is 0, 1 o~ 2~
~~~~ ' Examples of preferred bivalent hydrocarbon radicals rep'resented by R1 are the methylene and the ethylene radicals, ~as''well as the propylene, butylene, cyclohexylene, octadecylene, phenylene and butenylene radicals. Because of its availability, the n-propylene radical is the preferred radical.
The examples cited for the alkyl radicals represented by R are equally applicable to the alkyl radicals represented by R2. It is preferred that at least one R2 be hydrogen. Examples of suitable aminoalkyl radicals are hose of the general formulas:
2N(C 2)3 ~
N~CH~l2NH(C~2~3-' E12N ( CEI 2 ~ 2-- (H3C)2N(CH2)2-, ~2N(CH2)5-' H(N C 2C 2)3 C4HgNHCH2CH2NHCH2CH2~ ~
Examples of preferred alkyl radicals represented by R3 I are the methyl, the ethyl and the isopropyl radicals.
It is preferred that the organopolysiloxanes (1) of this invention have a viscosity of from 10 to 1,000 mPa.s at 25C, and more preferably from about 20 to 100 mPa.s at 25C.
It is possible to use only one type of organopolysiloxane (1), or a mixture of two or more different types of organopolysiloxane (1) may be used.
The organopolysiloxane (1) is preferably used in an ~~mount o from about o.i to 4 parts by weight for each 10 to 90 parts by weight of the diorganopolysiloxane (5) which contains an'Si-bonded hydroxyl group in each of its terminal units.
~J~
In the process of this invention it is possible to use as organopolysiloxanes (2) having at least 3 Si-bonded hydrogen atoms per molecule, the same orqanopolysiloxanes containing at least 3 Si-bonded hydrogen atoms per molecule, which has been or could have been used in all of the processes known heretofore for impregnating fibers with agueous emulsions.
In the organopolysiloxanes (2) having at least 3 Si-bonded hydrogen atoms per molecule, the silicon valences which are not saturated with hydrogen and siloxane-oxygen atoms, are preferably saturated by methyl, ethyl or phenyl radicals or a mixture containing at least two ~uch radicals~
The preferred organopolysiloxanes (2) having at least 3 Si-bonded hydrogen atoms per molecule are those of the general formula (C~3)3SiO(5iR2o)pSi(CH3)3, where R4 represents hydrogen or methyl, ethyl or phenyl radicals, and p is an integer having a value of from 10 to 500/ with the proviso that only one hydrogen atom may be bonded to each silicon atom and the ratio of R4Sio units wherein both R4s are hydro~
carbon radicals, to the R4HSi units, in which R4 is a hydrocarbon radical/ must be ~etween 3:1 and 1:4. Also, it is preferred that R4 be methyl when it is not hydrogen.
The organopolysiloxanes (2~ having at least 3 Si-bonded hydrogen atoms per molecule may contain the same or different molecules of this type of organopolysiloxaneO
The organopolysiloxane (2) ha~ing at least 3 Si-bonded hydrogen atoms per molecule is preferably used in an amount of from 1.2 to 12 parts by weight for each 10 to 90 parts by weight of the diorganopolysiloxane (5).
3~ In this in~ention, it is possible to use as condensa-tion catalysts (3) any catalysts which have been or could have ~een used heretofore in an aqueous emulsion for the condensation of Si-bonded condensable groups~ Preferred examples of such catalysts are carboxylic acid salts of tin or zinc in which hydrocarbon radicals may be bonded directly to such metals~
Suitable examples of condensation catalysts (3) are dibutyltin dilaurate, tin octoate, di 2-ethylhexyltin dilaurate, di n-butyltin di-2-ethylhexoate, di-2-ethylhexyltin di-2-ethylhexoate and zinc octoate. Additional examples of the condensation 3~5 catalysts (3) are alkoxy titanates, such as butyl ti-tanate and triethanolamine titanates, as well as zirconium compounds.
Only one type of condensation catalyst (3), need be used; however, a mixture consisting of at least two different S types of condensation catalyst (3), may be used, such as for example, a mixture containing a dibutyltin dilaurate and butyl titanate.
The condensation catalyst (3) is preferably employed in an amount of from about 0.3 to 6 parts by weight for each 10 ; ~o 90 parts by weight of the diorganopolysiloxane (5).
When it is desired to impart a high degree of hydro-phobicity to an impregnated textile material by this invention, then it is preferred that at least a part of the emulsifier ~4) contain an organosiloxane-oxyalkylene-block copolymer, in which the polyoxyalkylene block, or blocks are bonded to the organopoly-siloxane block or blocks through an SiOC bond (4a)O Preferred examples of such block copolymers (4a) are those consisting of dimethylpolysiloxane and polyoxyethylene or polyethylene glycol~
A~ the proportion of such block ~opolymers (4a) in the emulsifier (4) is increased, the degree of hydrophobicity imparted to the impregnated fibers likewise increases. Emulsifiers other than the organosiloxane-oxyalkylene-block copolymers ~4al having SiOC
bonds, which have beer. or could have been used heretofore in emulsifying organopolys~loxanes in water may be used in this invention. Examples of such emulsifiers (4b) are non-ionic emulsifiers, such as alkanol or phenol polyglycol ethers, or alkylphenols, such as polyoxyethylene alkylphenols, polyoxy-ethylene sorbitan hexastearate, polyoxyethylene isotridecylether, trimethyl nonyl ether of polyethylene glycol, containing from 6 to 14 ethylene oxide units per molecule, polyoxyethylene sorbitan oleate having a saponification number of from 102 to 108 and a hydroxyl number of from 25 to 35, and anionic emulsifiers such as sodium alkylarylpolyethylene glycol sulfonate.
The organosiloxane-oxyalkylene block copolymer (4a) ~avlng an SiOC bond is preferably used in an amount of from 0 to ~ ~0 parts by weight for each 10 to 90 parts by weight of diorgano-polysiloxane ~51.
; . .. . .. _ ~~~~~~~~~ T~e emulsi~fiers-(4bl~- other than the organosiloxane-oxyalkylene copolymer (4a) having an SiOC bond, are preferably 3~
used in an amount o~ from 0 to 20 parts by wei~Jht for each 10 t~
90 parts by weight of diorganopolysilo~ane (5).
It is preferred that the sum of the emulsifiers (4a) and (4b~ be at least 5 parts by weight for each 10 to gO parts by weight of the diorganopolysiloxane (5)O
Also, the preferred diorganopolysiloxanes (5) having an Si-bonded hydroxyl group in each of their terminal units and whose organic radicals are free of basic nitrogen atoms, can be repr~sented by the following general formula ~oSiR2o(SiR2o)n~, in which R is the same as above and n is an integer having a value such that the average viscosity of these diorganopoly-siloxanes (5) ranges from about 500 to 50,000 mPa~s at 25C, The examples cited for the R radicals of the diorganosiloxane units in the organopolysiloxane ~1) are équally applicable to the organic radicals of the organopolysiloxanz (5).
It is preferred that the viscosity of the organopoly-siloxane ~5) be from 2,000 to 10,000 mPa.s at 25C~
It is preferred that th~ sum of the constituents (1~
through (5) within the above parameters, amount to 100 parts by weight.
If it is desired to use the process of this invention to impart hydrophobic properties to impregnated fibers, then lt is preferred that still another subistance be utilized in this invention, namely a trimethylsiloxy end-blocked diorganopoly-siloxane (6) which has a viscosity of from 100 to 10,000 mPa.s at 25C and more preferably from 300 to 1,000 mPa.s at 25C.
The examples cited for the R radicals of the diorganosiloxane ~nits in organopolysiloxanie (1) are equally applicable to the organic radicals of the diorganosiloxane units of the organo-po~ysiloxanes (6).
Preferably the trimethylsiloxy end-blocked diorgano-polysiloxane (6) which has a viscosity of from 100 to 10,000 mPa.s at 25C is used in an amount of from about 0 to 90 parts by weight for each 10 to 90 parts by weight of the diorganopoly-siloxane t5)- Moreover, it is preferred that when the diorgano-; polysiloxane (6) is used in the emulsion that the constituents (1) throuyh (6), ~e used within the above parameters and that 3~
their sum amount to 100 parts by weight. The hydrophobic properW
ties of the fibers impregnated in accordance with the process of this invention increases as the amount of the trirnethylsiloxy / end-blocked diorganopolysiloxane (6) increases.
The so-called "crease-resistant compounds or finishes~
such as dimethyldihydroxyethylene urea (DMDHEU 1 containing zinc nitrate, may also be used in the ccmpositions of this invention especially when the fibers to be impregnated contain cellulose - or cotton fibers or mixtures of cellulose and cotton fibers.
In order to prevent premature crosslinking of the emulsions, it is preferred, where applicable, that emulsions containing organopolysiloxanes (1), (5) and (6), be prepared separately from the emulsions containing the organopolysiloxane havîng Si-bonded hydrogen (2), and the emulsions containing con densation catalyst (3) and that the resultant emulsions contain-ing the three different components be maintained separately until just prior to their intended use, at which time they should be mixed and, if necessary~ diluted with water and applied to the fibers.
The emulsions of this invention may be applied to the fibers by any of the methods generally used or Lmpregnating fibers with liquids, for example by immersion, coating, pouring, spraying, including aerosol spraying, rolling or padding~
It is preferred that the emulsions of this invention be applied in an amount such that after the water has evaporated,the fibers will increase in weight from about 1 to 20 percent by weight based on the original weight of the fibers~
The crosslinking or curing of the impregnated fibers takes place at room temperature, however~ it can be accelerated by heating the fibers to, for example, between about 50 and 180aC .
Fibers which have been rendered hydrophobic by the process of this invention are for example, useful in manufactur-ing rainwear. When the aqueous emulsion of this invention i5 used to impregnate keratin, it prevents or reduces shrinkage due to felting. Moreover, it imparts a soft and elastic feel to keratin, especially wool, which has been pretreated with chlor~
ine, rinsed and neutralized in accordance with the procedure described in Belgium Patent No. 651,439.
In the following examples, all parts and percentages axe by weiyht unless otherwise specified.
Example 1 A cotton fabric is immersed in an aqueous emulsion containing the following ingredients in addition to water:
72 parts of a dimethylpolysilox2ne having an Si~
bonded hydroxyl grouF in each of its terminal units in which the dimethylpolysiloxane has a viscosity of 5,000 mPa.s at 25C;
3 parts of a product obtained ~rom the reaction of a dimethylpolysiloxane containing an Si-bonded hydroxyl group in each of its terminal units and h~ving a viscosity of 100 mPa.s at 25C, with a silane of the formul~
H2N(CH2~2N~C~2)3si(ocH3)3, in which the reaction product has a viscosity of 40 mPa.s at 25C and an amine number of 3 as determined by the milliliters of 1 N HCl required to neutralize one gram o~ substance;
~0 11 parts of a trimethylsiloxy end-blocked organo-polysiloxane which consists of 75 mol percent of dimethylsiloxane units and 25 mol percent of methylhydrogen siloxane units and having a viscosity of 130 mPa.s at 25C;
6 parts of di-2-ethylhexyltin dilaurate;
8 parts of an alkanol polyglycol ether obtained fram the reaction o~ isotridecanol with ethylene oxide in a mol ration o lolO;
150 parts of dimethyldihydroxyethylene urea (DMDHEU);
and 56 parts of zinc nitrate;
with such an amount oE water in the emulsion, that 150 parts of DMD~EU are corresponding to a concentration of 4 percent in the emulsion. The fabric is squeezed until the amount of liquid ~b~ G ~
absorbed is equal to 100 percent of the weight of the fabric and then heated to 150C for 10 minutes.
The impregnated fabric thus obtained has a soft, elastic feel or '!handl' which is preserved even after the fabric has been laundered several times in an automatic washer at a temperature of 30~C. The f~bric is essentially non-hydrophobic.
Example 2 A fabric consisting of 35 percent cotton and 65 percent polyester is immersed in an aqueous emulsion containing the following ingredients in addition to water: ;
38 parts of a dimethylpolysiloxane containing an Si-bonded hydroxyl group in each of its terminal units and h~ing a viscosity of S,000 mPa~s at 25C;
41 parts of a trimethylsiloxy end-bloc~ed dimethyl-polysiloxane having a viscosity of 350 mPa.s at 25C;
A PROCESS FOR I~PRE~NATING ORGANIC FIBERS
The present invention relates to aqueous emulsions, particularly to aqueous emulsions which may be used for impreg-naking organic fibers. More particularlyl the invention relates t~ a process for impregnating fibers with an aqueous emulsion to impart a high degree of elasticity and a predetermined degree of hydrophobicity to the treated organic fibers.
Background of the Invention 9rganic fibers have been treated with aqueous emul sions containing polydiorganosiloxanes to impart hydrophobic propexties thereto. For example, U. S. Patent No. 4,098,701 to Burrill et al discloses treating organic fibers with an aqueous emulsion containing (A) an organopolysiloxane containing dior-ganosiloxane units in which the two organic radicals are mono-valent hydrocarbon radicals and further contains at least two monovalent SiC-bonded organic radicals with basic nitrcgen for each molecule, ~B) an organopolysiloxane having at least three silicon-bonded hydrogen atoms in the molecule and (C) a catalyst ~or the condensation of Si-bonded condensable groups.
In contrast to the processes known heretofore for txeating organic fibers, the process of this invention imparts not only a high degree of elasticity, but also a predetermined degree of hydrophobicity to the treated fibers. t~oreover, organic fibers treated in accordance with the process of thls invention have a high degree of dimensional stability and are easy to sew. Furthermore, all of the properties imparted to the treated organic fibers by the process of this invention ara preserved even when the fibers are washed with water or cleaned with organic solvents ~`~$3~
Therefore, it is an object of this invention to provide an aqueous emulsion for treating organic fibers~
Another object of this invention is to provide a process for treating organic fibers with an aqueous emulsior. to impart a high degree of elasticity to the treated fibers. Still another object of this invention is to provide a process for imparting a predetermined degree of hydrophobicity to the organic fibers. A
further object of this invention is to pxovide a process for imparting a high degree of dimensional stability to the treated O organic fibers. ~ - -~ ~~- `~- - ~
Swnmary of the In~ention The foregoing ob~ects and others which will become apparent from the following description are accomplished in accordance with this invention, generally speaking, by providing a process for impregnating organic fibers with an aqueous emul-sion comprising (l) an organopolysiloxane containing diorgano-siloxane units in which both organic radicals are monovalent hydrocarbon radicals, and also contains at least two monovalent SiC-bonded organic radicals per molecule with a basic nitrogen atom, in which the SiC-bonded organic radicals containing the basic nitrogen atom of the organopolysiloxane (l) are present in monoorganosiloxane units, (2~ an organopolysiloxane having at least 3 Si-bonded hydrogen atoms per molecule, (3) a catalyst for the condensation of Si-bonded condensable groups, (4) an emulsifier, (5) a diorganopolysiloxane containing an Si-bonded hydroxyl group in each of its terminal units, whose organic radicals are free of basic nitrogen atoms, and optionally (6) a trimethylsiloxy end-blocked diorganopolysiloxane having a vis-cosity of from about lO0 to lO,000 mPa.s at 25C.
Detailed Descrlption of the Invention Any organic fiber which has been or could have been impregnated heretofore with organopolysiloxanes can be impreg-nated with the aqueous emulsion of this invention.
Such organic fibers may be made of either natural or ~y~thetic fibers r- Suitable examples o organic fibers which may be ~reated by the process of this invention are fibers made of keratin, cotton, rayon, hemp, natural silk, polypropylene, polyethylene, polyester, polyurethane, polyamide, cellulose acetate and mixtures of such fibers. The fibers may be present --3~
in the form of fleeces, mats, ~abrics, knitted textiles, includ-ing articles of clothing or sections of clothing. Except for wool, it is preferred that the fibers be treated in the form of fabrics.
The amount of water present in these aqueous emulsions is not critical. It is, however, preferred that the total amount of water, in which the non-aqueous constitutents are dissolved or dispersed, range from about 35 to 90 percent by weight and more preferably rrom about 45 to 60 percent by ~eight, based on the total weight of the aqueous emulsion. These aqueous emulsions may be further diluted with water prior to application so that the amount of water will range from 60 to 99 percent by weight and more preferably from 80 to 95 percent by weight based on the total weight of the aqueous emulsion applied to the fabric.
The diorganosiloxane units present in the organopoly-siloxane (13 may be represented by the general formula R2Sib, in which R represents the same or different monovalent hydrocar bon radicals; preferably, having from 1 to 20 carbon atoms per radical. Examples of hydrocarbon radicals which may be present in the diorganosiloxane units of organopolysiloxane (1) are alkyl radicals, such as the methyl, ethyl, n-propyl and isopropyl radicals, as well as the butyl, octyl, tetradecyl and octadecyl radicals; alkenyl radicals such as the vinyl and the allyl radicals, as well as the hexenyl radicalsi cycloaliphatic hydro-carbon radicals, such as the cyclopentyl and the cyclohexyl radicals; aromatic hydrocarbon radicals such as the phenyl and the naphthyl radicals; alkaryl radicals such as the tolyl radicals and aralkyl radicals such as the benzyl radical.
Because of their availability, it is preferred that at least 80 percent of the number of hydrocarbon radicals in the diorgano-~iloxane units of organopolysiloxane (1) be methyl radicals.
The monoorganosiloxane units and the SiC-bonded organic radicals having a basic nitrogen atom which are present in the organopolysiloxane (1), may ke represented by the following general formula R2NR (R o)aSiO3_a I the above formula Rl represents a bivalent hydrocarbon radical, -R represents hydrogen or the same or different alkyl or amino-alkyl radicals, ~3 represents the same or different al};enyl radicals having from 1 to ~ carbon atoms per radical, and a is 0, 1 o~ 2~
~~~~ ' Examples of preferred bivalent hydrocarbon radicals rep'resented by R1 are the methylene and the ethylene radicals, ~as''well as the propylene, butylene, cyclohexylene, octadecylene, phenylene and butenylene radicals. Because of its availability, the n-propylene radical is the preferred radical.
The examples cited for the alkyl radicals represented by R are equally applicable to the alkyl radicals represented by R2. It is preferred that at least one R2 be hydrogen. Examples of suitable aminoalkyl radicals are hose of the general formulas:
2N(C 2)3 ~
N~CH~l2NH(C~2~3-' E12N ( CEI 2 ~ 2-- (H3C)2N(CH2)2-, ~2N(CH2)5-' H(N C 2C 2)3 C4HgNHCH2CH2NHCH2CH2~ ~
Examples of preferred alkyl radicals represented by R3 I are the methyl, the ethyl and the isopropyl radicals.
It is preferred that the organopolysiloxanes (1) of this invention have a viscosity of from 10 to 1,000 mPa.s at 25C, and more preferably from about 20 to 100 mPa.s at 25C.
It is possible to use only one type of organopolysiloxane (1), or a mixture of two or more different types of organopolysiloxane (1) may be used.
The organopolysiloxane (1) is preferably used in an ~~mount o from about o.i to 4 parts by weight for each 10 to 90 parts by weight of the diorganopolysiloxane (5) which contains an'Si-bonded hydroxyl group in each of its terminal units.
~J~
In the process of this invention it is possible to use as organopolysiloxanes (2) having at least 3 Si-bonded hydrogen atoms per molecule, the same orqanopolysiloxanes containing at least 3 Si-bonded hydrogen atoms per molecule, which has been or could have been used in all of the processes known heretofore for impregnating fibers with agueous emulsions.
In the organopolysiloxanes (2) having at least 3 Si-bonded hydrogen atoms per molecule, the silicon valences which are not saturated with hydrogen and siloxane-oxygen atoms, are preferably saturated by methyl, ethyl or phenyl radicals or a mixture containing at least two ~uch radicals~
The preferred organopolysiloxanes (2) having at least 3 Si-bonded hydrogen atoms per molecule are those of the general formula (C~3)3SiO(5iR2o)pSi(CH3)3, where R4 represents hydrogen or methyl, ethyl or phenyl radicals, and p is an integer having a value of from 10 to 500/ with the proviso that only one hydrogen atom may be bonded to each silicon atom and the ratio of R4Sio units wherein both R4s are hydro~
carbon radicals, to the R4HSi units, in which R4 is a hydrocarbon radical/ must be ~etween 3:1 and 1:4. Also, it is preferred that R4 be methyl when it is not hydrogen.
The organopolysiloxanes (2~ having at least 3 Si-bonded hydrogen atoms per molecule may contain the same or different molecules of this type of organopolysiloxaneO
The organopolysiloxane (2) ha~ing at least 3 Si-bonded hydrogen atoms per molecule is preferably used in an amount of from 1.2 to 12 parts by weight for each 10 to 90 parts by weight of the diorganopolysiloxane (5).
3~ In this in~ention, it is possible to use as condensa-tion catalysts (3) any catalysts which have been or could have ~een used heretofore in an aqueous emulsion for the condensation of Si-bonded condensable groups~ Preferred examples of such catalysts are carboxylic acid salts of tin or zinc in which hydrocarbon radicals may be bonded directly to such metals~
Suitable examples of condensation catalysts (3) are dibutyltin dilaurate, tin octoate, di 2-ethylhexyltin dilaurate, di n-butyltin di-2-ethylhexoate, di-2-ethylhexyltin di-2-ethylhexoate and zinc octoate. Additional examples of the condensation 3~5 catalysts (3) are alkoxy titanates, such as butyl ti-tanate and triethanolamine titanates, as well as zirconium compounds.
Only one type of condensation catalyst (3), need be used; however, a mixture consisting of at least two different S types of condensation catalyst (3), may be used, such as for example, a mixture containing a dibutyltin dilaurate and butyl titanate.
The condensation catalyst (3) is preferably employed in an amount of from about 0.3 to 6 parts by weight for each 10 ; ~o 90 parts by weight of the diorganopolysiloxane (5).
When it is desired to impart a high degree of hydro-phobicity to an impregnated textile material by this invention, then it is preferred that at least a part of the emulsifier ~4) contain an organosiloxane-oxyalkylene-block copolymer, in which the polyoxyalkylene block, or blocks are bonded to the organopoly-siloxane block or blocks through an SiOC bond (4a)O Preferred examples of such block copolymers (4a) are those consisting of dimethylpolysiloxane and polyoxyethylene or polyethylene glycol~
A~ the proportion of such block ~opolymers (4a) in the emulsifier (4) is increased, the degree of hydrophobicity imparted to the impregnated fibers likewise increases. Emulsifiers other than the organosiloxane-oxyalkylene-block copolymers ~4al having SiOC
bonds, which have beer. or could have been used heretofore in emulsifying organopolys~loxanes in water may be used in this invention. Examples of such emulsifiers (4b) are non-ionic emulsifiers, such as alkanol or phenol polyglycol ethers, or alkylphenols, such as polyoxyethylene alkylphenols, polyoxy-ethylene sorbitan hexastearate, polyoxyethylene isotridecylether, trimethyl nonyl ether of polyethylene glycol, containing from 6 to 14 ethylene oxide units per molecule, polyoxyethylene sorbitan oleate having a saponification number of from 102 to 108 and a hydroxyl number of from 25 to 35, and anionic emulsifiers such as sodium alkylarylpolyethylene glycol sulfonate.
The organosiloxane-oxyalkylene block copolymer (4a) ~avlng an SiOC bond is preferably used in an amount of from 0 to ~ ~0 parts by weight for each 10 to 90 parts by weight of diorgano-polysiloxane ~51.
; . .. . .. _ ~~~~~~~~~ T~e emulsi~fiers-(4bl~- other than the organosiloxane-oxyalkylene copolymer (4a) having an SiOC bond, are preferably 3~
used in an amount o~ from 0 to 20 parts by wei~Jht for each 10 t~
90 parts by weight of diorganopolysilo~ane (5).
It is preferred that the sum of the emulsifiers (4a) and (4b~ be at least 5 parts by weight for each 10 to gO parts by weight of the diorganopolysiloxane (5)O
Also, the preferred diorganopolysiloxanes (5) having an Si-bonded hydroxyl group in each of their terminal units and whose organic radicals are free of basic nitrogen atoms, can be repr~sented by the following general formula ~oSiR2o(SiR2o)n~, in which R is the same as above and n is an integer having a value such that the average viscosity of these diorganopoly-siloxanes (5) ranges from about 500 to 50,000 mPa~s at 25C, The examples cited for the R radicals of the diorganosiloxane units in the organopolysiloxane ~1) are équally applicable to the organic radicals of the organopolysiloxanz (5).
It is preferred that the viscosity of the organopoly-siloxane ~5) be from 2,000 to 10,000 mPa.s at 25C~
It is preferred that th~ sum of the constituents (1~
through (5) within the above parameters, amount to 100 parts by weight.
If it is desired to use the process of this invention to impart hydrophobic properties to impregnated fibers, then lt is preferred that still another subistance be utilized in this invention, namely a trimethylsiloxy end-blocked diorganopoly-siloxane (6) which has a viscosity of from 100 to 10,000 mPa.s at 25C and more preferably from 300 to 1,000 mPa.s at 25C.
The examples cited for the R radicals of the diorganosiloxane ~nits in organopolysiloxanie (1) are equally applicable to the organic radicals of the diorganosiloxane units of the organo-po~ysiloxanes (6).
Preferably the trimethylsiloxy end-blocked diorgano-polysiloxane (6) which has a viscosity of from 100 to 10,000 mPa.s at 25C is used in an amount of from about 0 to 90 parts by weight for each 10 to 90 parts by weight of the diorganopoly-siloxane t5)- Moreover, it is preferred that when the diorgano-; polysiloxane (6) is used in the emulsion that the constituents (1) throuyh (6), ~e used within the above parameters and that 3~
their sum amount to 100 parts by weight. The hydrophobic properW
ties of the fibers impregnated in accordance with the process of this invention increases as the amount of the trirnethylsiloxy / end-blocked diorganopolysiloxane (6) increases.
The so-called "crease-resistant compounds or finishes~
such as dimethyldihydroxyethylene urea (DMDHEU 1 containing zinc nitrate, may also be used in the ccmpositions of this invention especially when the fibers to be impregnated contain cellulose - or cotton fibers or mixtures of cellulose and cotton fibers.
In order to prevent premature crosslinking of the emulsions, it is preferred, where applicable, that emulsions containing organopolysiloxanes (1), (5) and (6), be prepared separately from the emulsions containing the organopolysiloxane havîng Si-bonded hydrogen (2), and the emulsions containing con densation catalyst (3) and that the resultant emulsions contain-ing the three different components be maintained separately until just prior to their intended use, at which time they should be mixed and, if necessary~ diluted with water and applied to the fibers.
The emulsions of this invention may be applied to the fibers by any of the methods generally used or Lmpregnating fibers with liquids, for example by immersion, coating, pouring, spraying, including aerosol spraying, rolling or padding~
It is preferred that the emulsions of this invention be applied in an amount such that after the water has evaporated,the fibers will increase in weight from about 1 to 20 percent by weight based on the original weight of the fibers~
The crosslinking or curing of the impregnated fibers takes place at room temperature, however~ it can be accelerated by heating the fibers to, for example, between about 50 and 180aC .
Fibers which have been rendered hydrophobic by the process of this invention are for example, useful in manufactur-ing rainwear. When the aqueous emulsion of this invention i5 used to impregnate keratin, it prevents or reduces shrinkage due to felting. Moreover, it imparts a soft and elastic feel to keratin, especially wool, which has been pretreated with chlor~
ine, rinsed and neutralized in accordance with the procedure described in Belgium Patent No. 651,439.
In the following examples, all parts and percentages axe by weiyht unless otherwise specified.
Example 1 A cotton fabric is immersed in an aqueous emulsion containing the following ingredients in addition to water:
72 parts of a dimethylpolysilox2ne having an Si~
bonded hydroxyl grouF in each of its terminal units in which the dimethylpolysiloxane has a viscosity of 5,000 mPa.s at 25C;
3 parts of a product obtained ~rom the reaction of a dimethylpolysiloxane containing an Si-bonded hydroxyl group in each of its terminal units and h~ving a viscosity of 100 mPa.s at 25C, with a silane of the formul~
H2N(CH2~2N~C~2)3si(ocH3)3, in which the reaction product has a viscosity of 40 mPa.s at 25C and an amine number of 3 as determined by the milliliters of 1 N HCl required to neutralize one gram o~ substance;
~0 11 parts of a trimethylsiloxy end-blocked organo-polysiloxane which consists of 75 mol percent of dimethylsiloxane units and 25 mol percent of methylhydrogen siloxane units and having a viscosity of 130 mPa.s at 25C;
6 parts of di-2-ethylhexyltin dilaurate;
8 parts of an alkanol polyglycol ether obtained fram the reaction o~ isotridecanol with ethylene oxide in a mol ration o lolO;
150 parts of dimethyldihydroxyethylene urea (DMDHEU);
and 56 parts of zinc nitrate;
with such an amount oE water in the emulsion, that 150 parts of DMD~EU are corresponding to a concentration of 4 percent in the emulsion. The fabric is squeezed until the amount of liquid ~b~ G ~
absorbed is equal to 100 percent of the weight of the fabric and then heated to 150C for 10 minutes.
The impregnated fabric thus obtained has a soft, elastic feel or '!handl' which is preserved even after the fabric has been laundered several times in an automatic washer at a temperature of 30~C. The f~bric is essentially non-hydrophobic.
Example 2 A fabric consisting of 35 percent cotton and 65 percent polyester is immersed in an aqueous emulsion containing the following ingredients in addition to water: ;
38 parts of a dimethylpolysiloxane containing an Si-bonded hydroxyl group in each of its terminal units and h~ing a viscosity of S,000 mPa~s at 25C;
41 parts of a trimethylsiloxy end-bloc~ed dimethyl-polysiloxane having a viscosity of 350 mPa.s at 25C;
2 par-ts of the reaction product described in Example 1, in which a dimethylpolysiloxane having an Si-bonded hydroxyl group in each of its texmlnal units is reacted with a silane of the fonmula ~2N~CH2)2NH(CH2)3Si(oCH3~3;
6 parts of the organopolysiloxane described in Example 1 having Si-bonded hydrogen;
2 parts di-2-ethylhexyltin dilaurate;
8 parts of a dimethylsiloxane-oxyethylene-block copolymer in which the polyoxyethylene block is bonded to the dimethylpolysiloxane block by an SiOC bond, wherein the mole ratio of dimethyl-~iloxane units to ethyiene oxide units is about 1:6.5 and the viscosity of the block copolymer is akout 250 raPa.s at 25C;
BC?~;
6 parts of the organopolysiloxane described in Example 1 having Si-bonded hydrogen;
2 parts di-2-ethylhexyltin dilaurate;
8 parts of a dimethylsiloxane-oxyethylene-block copolymer in which the polyoxyethylene block is bonded to the dimethylpolysiloxane block by an SiOC bond, wherein the mole ratio of dimethyl-~iloxane units to ethyiene oxide units is about 1:6.5 and the viscosity of the block copolymer is akout 250 raPa.s at 25C;
BC?~;
3 parts of the polyethylene glycol ether o iso-tridecanol, described in ~xample 1;
150 parts of dimethyldihydroxyethylene urea (DMDHEU~;
and 56 parts zinc nitrate;
with such an amount of water in the emulsion, that 150 parts of DMD~EU correspond to a concentration of 4 percent in the emul-sion. The fabric is squeezed until the amount of fluid absorbed ii~ equal to 100 percent of the weight of the fabric and heated for 10 minutes to 150C~
The impregnated fabric thus obtained has a soft and elastic feel and even after it has been laundered 5 times at 30C in an automatic washer, the feel or "hand~ is preserved.
The fabric 's water-repellency is tested in accordance with the so-called "Spray Testn IAATCC 22-1967). The following values are obtained:
Number of washings at 30C 0 1 3 S
Spray Test factor 100 100 100 80 Example 3 The procedure described in Example 2 is repeated, except that the dimethyldihydroxyethylene urea (DMDHEU), and zinc nitrate is omitted from the emulsionO Also, the amount of dimethylpolysiloxane containing an Si-bonded hydroxyl group in each of its terminal units corresponds to a concentration of 1.9 percent in the emulsion. A wool fabxic weighing approximately 400 g/m2 is substituted for the cotton-polyester mixed fabric and immersed in the emulsion.
The impregnated fabric thus obtained has dimensional ~tability and has a so~t and elastic feel. Its wat~r repellency potential in accordance with AATCC 22-1967 is approximately 90.
All of these properties remain essentially unaltered even after five washings in an automatic household washer at 30C
Example 4 The procedure described in Example 2 is repeated, except that the dimethyldihydroxyethylene urea (DMDHEU), and zinc nitrate has been cmitt~d from the emulsion. The amount of dimethylpolysiloxane containing an Si-bonded hydroxyl group in each of its terminal units corresponds to a concentration of 1.
percent in the emulsion, and a polyester knit is substituted or the cotton-polyester mixed fabric.
The impregnated fabric ob-tained has stable dimensions and a soft and elastic feel. Its water repellency in accordance ,/5 with test AATCC 22-1967 is between 90 and 100. All of these properties remain practically unaltered even after 5 washings in an automatic washer at 30C~
Example 5 A polyester knit is immersed in an aqueous emulsion ~0 containing the following ingredients in addition to water:
32 parts of a dimethylpolysiloxane containing an Si~
bonded hydroxyl group in each of its terminal units and having a viscosity of 5,000 mPa.s at 25C;
24 parts of a trimethylsiloxy end-blocked dimethyl-polysiloxane having a viscosity of 350 mPaOs at 25C;
2 parts of the reaction product described in Example 1, in which a dimethylpolysiloxane having an Si-bonded hydroxyl group in each of its terminal units is reacted with a silane of the formula ~;2N~CH2~2NH~CH2)3Si(ocH3)3;
8 parts of the organopolysiloxane described in ~xample 1 having Si-bonded hydrogen atoms;
150 parts of dimethyldihydroxyethylene urea (DMDHEU~;
and 56 parts zinc nitrate;
with such an amount of water in the emulsion, that 150 parts of DMD~EU correspond to a concentration of 4 percent in the emul-sion. The fabric is squeezed until the amount of fluid absorbed ii~ equal to 100 percent of the weight of the fabric and heated for 10 minutes to 150C~
The impregnated fabric thus obtained has a soft and elastic feel and even after it has been laundered 5 times at 30C in an automatic washer, the feel or "hand~ is preserved.
The fabric 's water-repellency is tested in accordance with the so-called "Spray Testn IAATCC 22-1967). The following values are obtained:
Number of washings at 30C 0 1 3 S
Spray Test factor 100 100 100 80 Example 3 The procedure described in Example 2 is repeated, except that the dimethyldihydroxyethylene urea (DMDHEU), and zinc nitrate is omitted from the emulsionO Also, the amount of dimethylpolysiloxane containing an Si-bonded hydroxyl group in each of its terminal units corresponds to a concentration of 1.9 percent in the emulsion. A wool fabxic weighing approximately 400 g/m2 is substituted for the cotton-polyester mixed fabric and immersed in the emulsion.
The impregnated fabric thus obtained has dimensional ~tability and has a so~t and elastic feel. Its wat~r repellency potential in accordance with AATCC 22-1967 is approximately 90.
All of these properties remain essentially unaltered even after five washings in an automatic household washer at 30C
Example 4 The procedure described in Example 2 is repeated, except that the dimethyldihydroxyethylene urea (DMDHEU), and zinc nitrate has been cmitt~d from the emulsion. The amount of dimethylpolysiloxane containing an Si-bonded hydroxyl group in each of its terminal units corresponds to a concentration of 1.
percent in the emulsion, and a polyester knit is substituted or the cotton-polyester mixed fabric.
The impregnated fabric ob-tained has stable dimensions and a soft and elastic feel. Its water repellency in accordance ,/5 with test AATCC 22-1967 is between 90 and 100. All of these properties remain practically unaltered even after 5 washings in an automatic washer at 30C~
Example 5 A polyester knit is immersed in an aqueous emulsion ~0 containing the following ingredients in addition to water:
32 parts of a dimethylpolysiloxane containing an Si~
bonded hydroxyl group in each of its terminal units and having a viscosity of 5,000 mPa.s at 25C;
24 parts of a trimethylsiloxy end-blocked dimethyl-polysiloxane having a viscosity of 350 mPaOs at 25C;
2 parts of the reaction product described in Example 1, in which a dimethylpolysiloxane having an Si-bonded hydroxyl group in each of its terminal units is reacted with a silane of the formula ~;2N~CH2~2NH~CH2)3Si(ocH3)3;
8 parts of the organopolysiloxane described in ~xample 1 having Si-bonded hydrogen atoms;
4 parts of di-2-ethylhexyltin dilaurate;
4 parts of the dimethylsiloxane-oxyethylene block copolymer described in Example 2;
and 6 parts of the polyethylene glycoi ether of isotricanol described in Example 1;
with such an amount of water in the emulsion,,that 32 parts of dimethylpolysiloxane containing an Si-bonded hydroxyl group in each of its terminal units correspond to a concentration of 1.7 p,ercent in the emulsion. The fabric is squeezed until the 2mount of fluid absorbed is equal to 100 percent of the weight of the fabric and then heated to 150C.
.~t~ 3~ ~ S
The properties of the impregnated fabric are the same as those of the knit treat~ in accordance with Example 4, except that the water-repellency as measured in accordance with test AATCC 22-1967 is only 80~ The degree of water-repellency
4 parts of the dimethylsiloxane-oxyethylene block copolymer described in Example 2;
and 6 parts of the polyethylene glycoi ether of isotricanol described in Example 1;
with such an amount of water in the emulsion,,that 32 parts of dimethylpolysiloxane containing an Si-bonded hydroxyl group in each of its terminal units correspond to a concentration of 1.7 p,ercent in the emulsion. The fabric is squeezed until the 2mount of fluid absorbed is equal to 100 percent of the weight of the fabric and then heated to 150C.
.~t~ 3~ ~ S
The properties of the impregnated fabric are the same as those of the knit treat~ in accordance with Example 4, except that the water-repellency as measured in accordance with test AATCC 22-1967 is only 80~ The degree of water-repellency
5' is unaltered even after 5 washings in an automatic washer at 30C.
Claims (9)
OR PRIVILEGE OF IS CLAIMED ARE DEFINED AS FOLLOWS:
1. An aqueous emulsion for impregnating organic fibers comprising (1) an organopolysiloxane having diorganosi-loxane units in which both organic radicals are monovalent hydrocarbon radicals, and at least two monovalent SiC-bonded organic radicals having a basic nitrogen atom per molecule, in which the SiC-bonded organic radicals having a basic nitrogen atom are present in monoorganosiloxane units; (2) an organopoly-siloxane with at least 3 Si-bonded hydrogen atoms per molecule;
and (3) a catalyst for the condensation of Si-bonded condensable groups; (4) an emulsifier; and (5) a diorganopolysiloxane having an Si-bonded hydroxyl group in each of its terminal units and whose organic radicals are free of nitrogen.
and (3) a catalyst for the condensation of Si-bonded condensable groups; (4) an emulsifier; and (5) a diorganopolysiloxane having an Si-bonded hydroxyl group in each of its terminal units and whose organic radicals are free of nitrogen.
2. A process for impregnating organic fibers which comprises applying to the organic fibers an aqueous emulsion containing (1) an organopolysiloxane having diorganosiloxane units in which both organic radicals are monovalent hydrocarbon radicals, and at least two monovalent SiC-bonded organic radicals having a basis nitrogen atom per molecule, in which the SiC-bonded organic radicals having a basic nitrogen atom are present in monoorganosiloxane units; (2) an organopolysiloxane with at least 3 Si-bonded hydrogen atoms per molecule; and (3) a catalyst for the condensation of Si-bonded condensable groups; (4) an emulsifier; and (5) a diorganopolysiloxane having an Si-bonded hydroxyl group in each of its terminal units and whose organic radicals are free of nitrogen.
3. The process of claim 2, wherein the aqueous emulsion contains (6) a trimethylsiloxy end-blocked diorgano-polysiloxane having a viscosity of from 100 to 10,000 mPa.s at 25°C.
-15- .
-15- .
4. The process of claims 2 or 3, wherein the aqueous emulsion contains a crease-resistant compound.
5. The process of claim 2, wherein the organopoly-siloxane (1) is present in an amount of from 0.4 to 4 parts by weight for each 10 to 90 parts by weight of the diorganopoly-siloxane (5).
6. The process of claim 2, wherein the organopoly-siloxane (2) is present in an amount of from 1.2 to 12 parts by weight for each 10 to 90 parts by weight of the diorganopoly-siloxane (5).
7. The process of claim 3, wherein the catalyst is present in an amount of from 0.3 to 6 parts by weight for each 10 to 90 parts by weight of the diorganopolysiloxane (5).
8. The process of claim 2, wherein the diorganopoly-siloxane (6) is present in an amount of from 0 to 90 parts by weight for each 10 to 90 parts by weight of the diorganopoly siloxane (5).
9. The process of claims 2 or 3, wherein the organic fiber is wool which has been treated with chlorine, rinsed and neutralized prior to being impregnated with the aqueous emulsion.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19813104582 DE3104582A1 (en) | 1981-02-10 | 1981-02-10 | "METHOD FOR IMPREGNATING TEXTILE AREAS" |
| DEP3104582.0 | 1981-02-10 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1193805A true CA1193805A (en) | 1985-09-24 |
Family
ID=6124428
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000395942A Expired CA1193805A (en) | 1981-02-10 | 1982-02-10 | Process for impregnating organic fibers |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US4436856A (en) |
| EP (1) | EP0057937B2 (en) |
| JP (1) | JPS607071B2 (en) |
| AT (1) | ATE8673T1 (en) |
| CA (1) | CA1193805A (en) |
| DE (2) | DE3104582A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4552910A (en) * | 1983-03-11 | 1985-11-12 | Wacker-Chemie Gmbh | Aqueous compositions containing an organosilicon compound |
| DE3332997A1 (en) * | 1983-09-13 | 1985-03-28 | Wacker-Chemie GmbH, 8000 München | METHOD FOR IMPREGNATING TEXTILES FROM ORGANIC FIBERS |
| DE3343575A1 (en) * | 1983-12-01 | 1985-10-03 | Wacker-Chemie GmbH, 8000 München | METHOD FOR PRODUCING AQUEOUS EMULSIONS |
| US4476278A (en) * | 1984-01-05 | 1984-10-09 | Toshiba Silicone Co., Ltd. | Dustproof film forming material |
| US4504541A (en) * | 1984-01-25 | 1985-03-12 | Toyo Boseki Kabushiki Kaisha | Antimicrobial fabrics having improved susceptibility to discoloration and process for production thereof |
| DE3503457A1 (en) * | 1985-02-01 | 1986-08-07 | Wacker-Chemie GmbH, 8000 München | METHOD FOR IMPREGNATING ORGANIC FIBERS |
| US4678815A (en) * | 1985-06-27 | 1987-07-07 | Stauffer-Wacker Silicones Corporation | Aqueous silicone emulsions as bladder lubricants |
| US4840742A (en) * | 1987-02-13 | 1989-06-20 | Wacker Silicones Corporation | Silicone containing emulsions as bladder lubricants |
| DE3723697A1 (en) * | 1987-04-24 | 1988-11-17 | Pfersee Chem Fab | AQUEOUS, FINE-PARTIC TO OPTICALLY CLEAR, THERMALLY AND MECHANICALLY STABLE SILICONE EMULSIONS, METHOD FOR THE PRODUCTION AND USE THEREOF |
| US4888384A (en) * | 1987-10-21 | 1989-12-19 | General Electric Company | Stable, two package water emulsions of silicone hydride fluids |
| US5126072A (en) * | 1987-10-21 | 1992-06-30 | General Electric Company | Stable, two package water emulsions of silicone hydride fluids |
| US4781973A (en) * | 1987-10-22 | 1988-11-01 | General Electric Company | Fabric coating |
| US4874431A (en) * | 1988-07-14 | 1989-10-17 | Dow Corning Corporation | Low volatility water repellents |
| JPH07767B2 (en) * | 1989-01-31 | 1995-01-11 | 信越化学工業株式会社 | Polish |
| US5000861A (en) * | 1989-08-23 | 1991-03-19 | Union Carbide Chemicals And Plastics Co. Inc. | Stable emulsions containing amino polysiloxanes and silanes for treating fibers and fabrics |
| DE4004946A1 (en) * | 1990-02-16 | 1991-08-22 | Wacker Chemie Gmbh | FINE-PART ORGANOPOLYSILOXANE EMULSIONS |
| KR100246598B1 (en) * | 1991-12-07 | 2000-04-01 | 브라이언마크그레이 | Casting of light metal alloys |
| DE19857106C2 (en) * | 1998-12-10 | 2000-10-26 | Heinz Neubaur | Swimwear made from a water-repellent fabric and process for its manufacture |
| IN2014MN02260A (en) * | 2012-05-24 | 2015-07-24 | Momentive Performance Mat Inc | |
| WO2015083227A1 (en) * | 2013-12-03 | 2015-06-11 | Ｋｂツヅキ株式会社 | Modified fiber and method for producing same |
| SE542554C2 (en) * | 2016-09-06 | 2020-06-02 | Organoclick Ab | Emulsified liquid composition comprising amino functional siloxane and uses therof |
| JP7300395B2 (en) * | 2017-12-25 | 2023-06-29 | 日華化学株式会社 | Water repellent composition and method for producing water repellent textile product |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2838423A (en) * | 1957-05-29 | 1958-06-10 | Dow Corning | Amidomethyl quaternary ammonium siloxanes and a method of rendering fabrics water repllent therewith |
| FR1419968A (en) * | 1963-12-07 | 1965-12-03 | Shinetsu Chem Ind Co | Improvements to the compositions and processes for waterproofing fabrics |
| DE1594953A1 (en) * | 1966-05-28 | 1969-07-03 | Rotta Chem Fab Theodor | Process for finishing fiber material with polysiloxanes |
| GB1543157A (en) * | 1975-05-17 | 1979-03-28 | Dow Corning Ltd | Treatment of fibres |
| GB1570983A (en) | 1976-06-26 | 1980-07-09 | Dow Corning Ltd | Process for treating fibres |
| US4167501A (en) | 1978-04-13 | 1979-09-11 | Dow Corning Corporation | Process for preparing a textile-treating composition and resin-silicone compositions therefor |
| US4152273A (en) * | 1978-07-18 | 1979-05-01 | Arkansas Co., Inc. | Soil releasable hydrophilic surface finish for textile fabrics |
| CA1134986A (en) * | 1978-11-08 | 1982-11-02 | Peter M. Burrill | Organosilicon polymers |
| GB2075040B (en) * | 1980-04-08 | 1983-11-23 | Dow Corning Ltd | Organopolysiloxane compositions |
| DE3014675A1 (en) * | 1980-04-16 | 1981-10-29 | Chemische Fabrik Pfersee Gmbh, 8900 Augsburg | METHOD FOR THE DIMENSIONAL STABILIZATION OF AREA-SHAPED TEXTILE MATERIALS |
-
1981
- 1981-02-10 DE DE19813104582 patent/DE3104582A1/en not_active Withdrawn
-
1982
- 1982-02-08 US US06/346,457 patent/US4436856A/en not_active Expired - Lifetime
- 1982-02-09 JP JP57018288A patent/JPS607071B2/en not_active Expired
- 1982-02-10 DE DE8282100947T patent/DE3260418D1/en not_active Expired
- 1982-02-10 EP EP19820100947 patent/EP0057937B2/en not_active Expired
- 1982-02-10 CA CA000395942A patent/CA1193805A/en not_active Expired
- 1982-02-10 AT AT82100947T patent/ATE8673T1/en active
Also Published As
| Publication number | Publication date |
|---|---|
| EP0057937A3 (en) | 1982-09-01 |
| JPS607071B2 (en) | 1985-02-22 |
| DE3260418D1 (en) | 1984-08-30 |
| EP0057937A2 (en) | 1982-08-18 |
| EP0057937B1 (en) | 1984-07-25 |
| JPS57149563A (en) | 1982-09-16 |
| DE3104582A1 (en) | 1982-09-02 |
| EP0057937B2 (en) | 1986-12-30 |
| ATE8673T1 (en) | 1984-08-15 |
| US4436856A (en) | 1984-03-13 |
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